U.S. patent application number 17/442953 was filed with the patent office on 2022-03-31 for high wet fast disperse dye mixtures of n-[4-(5-thiocyanato-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and n-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives.
The applicant listed for this patent is DyStar Colours Distribution GmbH. Invention is credited to Clemens GRUND, Manfred HOPPE, Chongjun JIAO, Adrian MURGATROYD, Fanny VERMANDEL.
Application Number | 20220098416 17/442953 |
Document ID | / |
Family ID | |
Filed Date | 2022-03-31 |
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United States Patent
Application |
20220098416 |
Kind Code |
A1 |
MURGATROYD; Adrian ; et
al. |
March 31, 2022 |
HIGH WET FAST DISPERSE DYE MIXTURES OF
N-[4-(5-THIOCYANATO-2,4-DINITRO-PHENYLAZO)-PHENYL]-AMINE
DERIVATIVES AND N-[4-(4-NITRO-PHENYLAZO)-PHENYL]-AMINE
DERIVATIVES
Abstract
The present invention is directed to dye mixtures comprising
dyes of formula (1) and dyes of formula (2), the process of the
production and the use of the dye mixtures. ##STR00001##
Inventors: |
MURGATROYD; Adrian;
(Macclesfield, GB) ; HOPPE; Manfred; (Kurten,
DE) ; GRUND; Clemens; (Hattersheim, DE) ;
VERMANDEL; Fanny; (Wiesbaden, DE) ; JIAO;
Chongjun; (Shanghai, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DyStar Colours Distribution GmbH |
Raunheim |
|
DE |
|
|
Appl. No.: |
17/442953 |
Filed: |
March 12, 2020 |
PCT Filed: |
March 12, 2020 |
PCT NO: |
PCT/EP2020/056623 |
371 Date: |
September 24, 2021 |
International
Class: |
C09B 67/22 20060101
C09B067/22 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 27, 2019 |
EP |
1916550.9 |
Claims
1. A dye mixture comprising at least one dye of formula (1)
##STR00034## wherein independent of each other R.sup.1 is hydrogen,
(C.sub.1-C.sub.4)-alkyl or C.sub.1-C.sub.4-alkoxy, R.sup.2 is
hydrogen, carboxy, (C.sub.1-C.sub.4)-alkyl, halogen, acylamino,
--NHCO-aryl, --NHCO-benzyl) or sulfonylamino, R.sup.3 and R.sup.4
is hydrogen, (C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n-phenyl,
CH.sub.2--CH.dbd.CH.sub.2, (CH.sub.2).sub.n--OH,
(CH.sub.2).sub.n--O--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O-phenyl, (CH.sub.2).sub.n--O-benzyl,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--OH,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--O-phenyl,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--O-benzyl,
(CH.sub.2).sub.n--COOH,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, (CH.sub.2).sub.n--O--CO-benzyl,
COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl,
CHR.sup.9--(CH.sub.2).sub.p--(C.sub.1-C.sub.4)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p phenyl, CHR.sup.9--CH.dbd.CH.sub.2,
CHR.sup.9--(CH.sub.2).sub.p--OH,
CHR.sup.9--(CH.sub.2).sub.p--O--(C.sub.1-C.sub.4)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--O-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--OH,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.4)-al-
kyl, CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--COOH,
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.4)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--COO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--COO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--CN,
CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.4)-a-
lkyl, CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO--(C.sub.1-C.sub.4)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p-2-furfuryl or
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.n-2-furfuryl,
wherein R.sup.9 is (C.sub.1-C.sub.4)-alkyl or
(C.sub.1-C.sub.4)-alkyl substituted by --OH or halogen, n is 1 to
4, m is 1 to 4 and p is 0 to 3, with the proviso that at least one
of R.sup.3 and R.sup.4 is not hydrogen, and at least one dye of
formula (2) ##STR00035## wherein independent of each other R.sup.5
and R.sup.6 is hydrogen, (C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n-phenyl, CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.n--OH, (CH.sub.2).sub.n--O--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O-phenyl, (CH.sub.2).sub.n--O-benzyl,
(CH.sub.2)--O--(CH.sub.2).sub.m--OH,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2)--O--(CH.sub.2).sub.m--O-phenyl,
(CH.sub.2)--O--(CH.sub.2).sub.m--O-benzyl, (CH.sub.2).sub.n--COOH,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, (CH.sub.2).sub.n--O--CO-benzyl,
COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 to
4 and m is 1 to 4, with the proviso that at least one of R.sup.5
and R.sup.6 is not hydrogen, R.sup.10 is hydrogen,
(C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkoxy, R.sup.11 is
hydrogen, carboxy, (C.sub.1-C.sub.4)-alkyl, halogen, acylamino,
--NHCO-aryl, --NHCO-benzyl) or sulfonylamino, X.sup.5 and X.sup.6
is hydrogen, halogen, nitro or cyano, with the proviso that at
least one of X.sup.5 and X.sup.6 is not hydrogen and L is hydrogen
or in case X.sup.6 is nitro and X.sup.5 is hydrogen L is hydrogen
or fluoro.
2. The dye mixture according to claim 1, wherein independent of
each other in the at least one dye of formula (1) R.sup.1 is
hydrogen, methyl or methoxy, R.sup.2 is hydrogen, hydroxy, COOH,
COO--(C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkyl,
--NHCO--(C.sub.1-C.sub.2)-alkyl, --NHCO-aryl, --NHCO-benzyl or
--NHSO.sub.2--(C.sub.1-C.sub.2)-alkyl, R.sup.3 and R.sup.4 is
hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-phenyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-benzyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, (CH.sub.2).sub.n--O--CO-benzyl,
COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl,
CHR.sup.9--CH.dbd.CH.sub.2,
CHR.sup.9--(CH.sub.2).sub.p--O--(C.sub.1-C.sub.2)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--O-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-al-
kyl, CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--COO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--COO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--CN,
CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-a-
lkyl, CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO--(C.sub.1-C.sub.2)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO-phenyl or
CHR.sup.9--(CH.sub.2).sub.p--O--CO-benzyl, wherein R.sup.9 is
(C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkyl substituted by
--OH or halogen, n is 1 or 2, m is 1 or 2 and p is 0 or 1, with the
proviso that at least one of R.sup.3 and R.sup.4 is not
hydrogen.
3. The dye mixture according to claim 1, wherein independent of
each other in the at least one dye of formula (1) R.sup.1 is
hydrogen or methoxy, R.sup.2 is hydrogen, methyl or
--NHCO--(C.sub.1-C.sub.2)-alkyl, R.sup.3 and R.sup.4 is hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl,
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl, wherein
R.sup.9 is (C.sub.1-C.sub.4)-alkyl, n is 1 or 2, m is 1 or 2 and
with the proviso that at least one of R.sup.3 and R.sup.4 is not
hydrogen
4. The dye mixture according to claim 1, wherein the at least one
dye of formula (1) is a dye of formula (1a) ##STR00036## wherein
independent from each other R.sup.3 and R.sup.4 is hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl or
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl, wherein
R.sup.9 is (C.sub.1-C.sub.4)-alkyl, n is 1 or 2, m is 1 or 2 and p
is 0 or 1, with the proviso that at least one of R.sup.3 and
R.sup.4 is not hydrogen and R.sup.7 and R.sup.8 is ethyl or
methyl.
5. The dye mixture according to claim 1, wherein the at least one
dye of formula (1) is a dye of formula (1b) ##STR00037## wherein
independent from each other R.sup.3 and R.sup.4 is hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl or
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl, wherein
R.sup.9 is (C.sub.1-C.sub.4)-alkyl, n is 1 or 2 and m is 1 or 2, p
is 0 or 1, with the proviso that at least one of R.sup.3 and
R.sup.4 is not hydrogen and R.sup.7 is ethyl or methyl.
6. The dye mixture according to claim 1, wherein the at least one
dye of formula (1) is a dye of formula (1c) ##STR00038## wherein
independent from each other R.sup.3 and R.sup.4 is hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl or
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl, wherein
R.sup.9 is (C.sub.1-C.sub.4)-alkyl, n is 1 or 2, m is 1 or 2 and p
is 0 or 1, with the proviso that at least one of R.sup.3 and
R.sup.4 is not hydrogen.
7. The dye mixture according to claim 1, wherein the at least one
dye of formula (1) is selected from the group consisting of
##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043##
##STR00044## ##STR00045## ##STR00046##
8. The dye mixture according to claim 1, wherein independent of
each other in the at least one dye of formula (2) R.sup.5 and
R.sup.6 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-phenyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-benzyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, (CH.sub.2).sub.n--O--CO-benzyl,
COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or
2 and m is 1 or 2, with the proviso that at least one of R.sup.5
and R.sup.6 is not hydrogen, R.sup.10 is hydrogen, methyl or
methoxy, R.sup.11 is hydrogen, hydroxy, COOH,
COO--(C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkyl,
--NHCO--(C.sub.1-C.sub.2)-alkyl, --NHCO-aryl, --NHCO-benzyl or
--NHSO.sub.2--(C.sub.1-C.sub.2)-alkyl, X.sup.5 and X.sup.6 is
hydrogen, chloro, bromo, nitro or cyano, with the proviso that at
least one of X.sup.5 and X.sup.6 is not hydrogen, and L is hydrogen
or in case X.sup.6 is nitro and X.sup.5 is hydrogen L is hydrogen
or fluoro.
9. The dye mixture according to claim 1, wherein independent of
each other in the at least one dye of formula (2) R.sup.5 and
R.sup.6 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or
2 and m is 1 or 2, with the proviso that at least one of R.sup.5
and R.sup.6 is not hydrogen, R.sup.10 is hydrogen or methoxy,
R.sup.11 is hydrogen, methyl or --NHCO--(C.sub.1-C.sub.2)-alkyl,
X.sup.5 and X.sup.6 is hydrogen, bromo, chloro, nitro or cyano,
with the proviso that at least one of X.sup.5 and X.sup.6 is not
hydrogen and L is hydrogen or in case X.sup.6 is nitro and X.sup.5
is hydrogen L is hydrogen or fluoro.
10. The dye mixture according to claim 1, wherein the at least one
dye of formula (2) is a dye of formula (2a) ##STR00047## wherein
independent from each other R.sup.5 and R.sup.6 are hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or
2 and m is 1 or 2, with the proviso that at least one of R.sup.5
and R.sup.6 is not hydrogen, R.sup.7 and R.sup.8 is ethyl or
methyl, X.sup.5 is hydrogen, bromo, chloro, nitro or cyano, X.sup.6
is hydrogen, nitro or cyano, with the proviso that X.sup.5 and
X.sup.6 are not both nitro and L is hydrogen or in case X.sup.6 is
nitro and X.sup.5 is hydrogen L is hydrogen or fluoro.
11. The dye mixture according to claim 1, wherein the at least one
dye of formula (2) is a dye of formula (2b) ##STR00048## R.sup.5
and R.sup.6 are hydrogen, (C.sub.1-C.sub.2)-alkyl,
(CH.sub.2)-phenyl, CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or
2 and m is 1 or 2, with the proviso that at least one of R.sup.5
and R.sup.6 is not hydrogen, R.sup.7 is ethyl or methyl and X.sup.5
is hydrogen, bromo, chloro, nitro or cyano, X.sup.6 is hydrogen,
nitro or cyano, with the proviso that X.sup.5 and X.sup.6 are not
both nitro and L is hydrogen or in case X.sup.6 is nitro and
X.sup.5 is hydrogen L is hydrogen or fluoro.
12. The dye mixture according to claim 1, wherein the at least one
dye of formula (2) is a dye of formula (2c) ##STR00049## wherein
independent from each other R.sup.2 is hydrogen or
--NHCO--(C.sub.1-C.sub.2)-alkyl, R.sup.5 and R.sup.6 is hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or
2 and m is 1 or 2 with the proviso that at least one of R.sup.5 and
R.sup.6 is not hydrogen, X.sup.5 and X.sup.6 is bromo or
chloro,
13. The dye mixture according to claim 1, wherein the at least one
dye of formula (2) is a dye of formula (2d) ##STR00050## wherein
independent from each other R.sup.5 and R.sup.6 is hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or
2 and m is 1 or 2 with the proviso that at least one of R.sup.5 and
R.sup.6 is not hydrogen, R.sup.7 is ethyl or methyl, R.sup.10 is
hydrogen, methyl or methoxy, X.sup.6 is chloro, bromo, nitro or
cyano and L is hydrogen or in case X.sup.6 is nitro L is hydrogen
or fluoro.
14. The dye mixture according to claim 1, wherein the at least one
dye of formula (2) is selected from the group consisting of
##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055##
##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060##
Description
[0001] This invention relates to high wet fast Rhodano-Disperse azo
dye mixtures.
[0002] Disperse-azo-dyes (1) with the substitution pattern
2,4,5--in the diazo-component are known e.g. from U.S. Pat. No.
4,619,993, DD209641, GB 2 020 680, U.S. Pat. No. 4,379,819, WO
2005/056690, WO 2005/040283 and WO 2016/041849. Dyes with general
Structure (2) and their mixtures are also known, --e.g. from EP 0
864 615, EP 0 894 830, EP 0 555 179, WO 2006/131530 and WO
2002/081572, but they have unsatisfactory build up properties for
deeper shades and/or insufficient wash- and contact-fastnesses.
[0003] It was now found that certain combinations of azo dyes of
the formula (1) together with dyes of formula (2) result in
improved build up and good wash- and contact-fastness properties on
polyester and polyester blends especially on
polyester-elastane/polyester-spandex.
[0004] The present invention thus is directed to a dye mixture
comprising at least one dye of formula (1)
##STR00002##
wherein independent of each other R.sup.1 is hydrogen,
(C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkoxy, R.sup.2 is
hydrogen, carboxy, (C.sub.1-C.sub.4)-alkyl, halogen, acylamino,
--NHCO-aryl, --NHCO-benzyl or sulfonylamino, R.sup.3 and R.sup.4 is
hydrogen, (C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n-phenyl,
CH.sub.2--CH.dbd.CH.sub.2, (CH.sub.2).sub.n--OH,
(CH.sub.2).sub.n--O--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O-phenyl, (CH.sub.2).sub.n--O-benzyl,
(CH.sub.2)--O--(CH.sub.2).sub.m--OH,
(CH.sub.2)--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--O-phenyl,
(CH.sub.2)--O--(CH.sub.2).sub.m--O-benzyl, (CH.sub.2).sub.n--COOH,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, (CH.sub.2).sub.n--O--CO-benzyl,
COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl,
CHR.sup.9--(CH.sub.2)--(C.sub.1-C.sub.4)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p phenyl, CHR.sup.9--CH.dbd.CH.sub.2,
CHR.sup.9--(CH.sub.2).sub.p--OH,
CHR.sup.9--(CH.sub.2).sub.p--O--(C.sub.1-C.sub.4)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--O-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--OH,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.4)-al-
kyl, CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--COOH,
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.4)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--COO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--COO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--CN,
CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.4)-a-
lkyl, CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO--(C.sub.1-C.sub.4)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p-2-furfuryl or
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.n-2-furfuryl, [0005]
wherein [0006] R.sup.9 is (C.sub.1-C.sub.4)-alkyl or
(C.sub.1-C.sub.4)-alkyl substituted by --OH or halogen, [0007] n is
1 to 4, [0008] m is 1 to 4 and [0009] p is 0 to 3, with the proviso
that at least one of R.sup.3 and R.sup.4 is not hydrogen, and at
least one dye of formula (2)
##STR00003##
[0009] wherein independent of each other R.sup.5 and R.sup.6 is
hydrogen, (C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n-phenyl,
CH.sub.2--CH.dbd.CH.sub.2, (CH.sub.2).sub.n--OH,
(CH.sub.2).sub.n--O--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O-phenyl, (CH.sub.2).sub.n--O-benzyl,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--OH,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--O-phenyl,
(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--O-benzyl,
(CH.sub.2).sub.n--COOH,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.4)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, (CH.sub.2).sub.n--O--CO-benzyl,
COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, [0010] wherein
[0011] n is 1 to 4 and [0012] m is 1 to 4, with the proviso that at
least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.10 is
hydrogen, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkoxy,
R.sup.11 is hydrogen, carboxy, (C.sub.1-C.sub.4)-alkyl, halogen,
acylamino, --NHCO-aryl, --NHCO-benzyl or sulfonylamino, X.sup.5 and
X.sup.6 is hydrogen, halogen, nitro or cyano, with the proviso that
at least one of X.sup.5 and X.sup.6 is not hydrogen and L is
hydrogen or in case X.sup.6 is nitro and X.sup.5 is hydrogen L is
hydrogen or fluoro.
[0013] Regarding both, dyes of formula (1) as well as dyes of
formula (2), there exist preferred ones to form overall preferred
combinations:
[0014] As to the selection of dyes of formula (1) a dye mixture as
described above is preferred, wherein independent of each other in
the at least one dye of formula (1)
R.sup.1 is hydrogen, methyl or methoxy, R.sup.2 is hydrogen,
hydroxy, COOH, COO--(C.sub.1-C.sub.2)-alkyl,
(C.sub.1-C.sub.2)-alkyl, --NHCO--(C.sub.1-C.sub.2)-alkyl,
--NHCO-aryl, --NHCO-benzyl or
--NHSO.sub.2--(C.sub.1-C.sub.2)-alkyl, R.sup.3 and R.sup.4 is
hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-phenyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-benzyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, (CH.sub.2).sub.n--O--CO-benzyl,
COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl,
CHR.sup.9--CH.dbd.CH.sub.2,
CHR.sup.9--(CH.sub.2).sub.p--O--(C.sub.1-C.sub.2)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--O-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-al-
kyl, CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--O--(CH.sub.2).sub.m--O-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--COO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--COO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--CN,
CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-a-
lkyl, CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO-phenyl,
CHR.sup.9--(CH.sub.2).sub.p--COO(CH.sub.2).sub.m--CO-benzyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO--(C.sub.1-C.sub.2)-alkyl,
CHR.sup.9--(CH.sub.2).sub.p--O--CO-phenyl or
CHR.sup.9--(CH.sub.2).sub.p--O--CO-benzyl, [0015] wherein [0016]
R.sup.9 is (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkyl
substituted by --OH or halogen, [0017] n is 1 or 2, [0018] m is 1
or 2 and [0019] p is 0 or 1, with the proviso that at least one of
R.sup.3 and R.sup.4 is not hydrogen.
[0020] More preferred is a dye mixture as described above, wherein
independent of each other in the at least one dye of formula
(1)
R.sup.1 is hydrogen or methoxy, R.sup.2 is hydrogen, methyl or
--NHCO--(C.sub.1-C.sub.2)-alkyl, R.sup.3 and R.sup.4 is hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl,
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl, [0021]
wherein [0022] R.sup.9 is (C.sub.1-C.sub.4)-alkyl [0023] n is 1 or
2, [0024] m is 1 or 2 and with the proviso that at least one of
R.sup.3 and R.sup.4 is not hydrogen.
[0025] A dye mixture as described above, wherein the at least one
dye of formula (1) is a dye of formula (1a)
##STR00004##
wherein independent from each other R.sup.3 and R.sup.4 is
hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl or
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl, [0026]
wherein [0027] R.sup.9 is (C.sub.1-C.sub.4)-alkyl, [0028] n is 1 or
2, [0029] m is 1 or 2 and [0030] p is 0 or 1, with the proviso that
at least one of R.sup.3 and R.sup.4 is not hydrogen and R.sup.7 and
R.sup.8 is ethyl or methyl, forms a preferred embodiment of the
present invention.
[0031] A dye mixture as described above, wherein the at least one
dye of formula (1) is a dye of formula (1b)
##STR00005##
wherein independent from each other R.sup.3 and R.sup.4 is
hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl or
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl, [0032]
wherein [0033] R.sup.9 is (C.sub.1-C.sub.4)-alkyl, [0034] n is 1 or
2, [0035] m is 1 or 2 and [0036] p is 0 or 1, with the proviso that
at least one of R.sup.3 and R.sup.4 is not hydrogen and R.sup.7 is
ethyl or methyl, forms a preferred embodiment of the present
invention.
[0037] A dye mixture as described above, wherein the at least one
dye of formula (1) is a dye of formula (1c)
##STR00006##
wherein independent from each other R.sup.3 and R.sup.4 is
hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl,
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl or
CHR.sup.9--(CH.sub.2).sub.p--COO--(C.sub.1-C.sub.2)-alkyl, [0038]
wherein [0039] R.sup.9 is (C.sub.1-C.sub.4)-alkyl, [0040] n is 1 or
2, [0041] m is 1 or 2 and [0042] p is 0 or 1, with the proviso that
at least one of R.sup.3 and R.sup.4 is not hydrogen, forms yet
another preferred embodiment of the present invention.
[0043] Most preferred is a dye mixture as described above, wherein
the at least one dye of formula (1) is selected from the group
consisting of
##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011##
##STR00012## ##STR00013## ##STR00014##
[0044] As to the selection of dyes of formula (2) a dye mixture as
described above is preferred, wherein independent of each other in
the at least one dye of formula (2)
[0045] R.sup.5 and R.sup.6 is hydrogen, (C.sub.1-C.sub.2)-alkyl,
(CH.sub.2)-phenyl, CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-phenyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-benzyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, (CH.sub.2).sub.n--O--CO-benzyl,
COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, [0046] wherein
[0047] n is 1 or 2 and [0048] m is 1 or 2, with the proviso that at
least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.10 is
hydrogen, methyl or methoxy, R.sup.11 is hydrogen, hydroxy, COOH,
COO--(C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkyl,
--NHCO--(C.sub.1-C.sub.2)-alkyl, --NHCO-aryl, --NHCO-benzyl or
--NHSO.sub.2--(C.sub.1-C.sub.2)-alkyl, X.sup.5 and X.sup.6 is
hydrogen, chloro, bromo, nitro or cyano, with the proviso that at
least one of X.sup.5 and X.sup.6 is not hydrogen and L is hydrogen
or in case X.sup.6 is nitro and X.sup.5 is hydrogen L is hydrogen
or fluoro.
[0049] More preferred is a dye mixture as described above, wherein
independent of each other in the at least one dye of formula
(2)
R.sup.5 and R.sup.6 is hydrogen, (C.sub.1-C.sub.2)-alkyl,
(CH.sub.2)-phenyl, CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, [0050] wherein
[0051] n is 1 or 2 and [0052] m is 1 or 2, with the proviso that at
least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.10 is
hydrogen or methoxy, R.sup.11 is hydrogen, methyl or
--NHCO--(C.sub.1-C.sub.2)-alkyl, X.sup.5 and X.sup.6 is hydrogen,
bromo, chloro, nitro or cyano, with the proviso that at least one
of X.sup.5 and X.sup.6 is not hydrogen and L is hydrogen or in case
X.sup.6 is nitro and X.sup.5 is hydrogen L is hydrogen or
fluoro.
[0053] A dye mixture as described above, wherein the at least one
dye of formula (2) is a dye of formula (2a)
##STR00015##
wherein independent from each other R.sup.5 and R.sup.6 is
hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, [0054] wherein
[0055] n is 1 or 2 and [0056] m is 1 or 2, with the proviso that at
least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.7 and
R.sup.8 is ethyl or methyl, X.sup.5 is hydrogen, bromo, chloro,
nitro or cyano, X.sup.6 is hydrogen, nitro or cyano, with the
proviso that X.sup.5 and X.sup.6 are not both nitro and L is
hydrogen or in case X.sup.6 is nitro and X.sup.5 is hydrogen L is
hydrogen or fluoro, forms a preferred embodiment of the present
invention.
[0057] A dye mixture as described above, wherein the at least one
dye of formula (2) is a dye of (2) is a dye of formula (2b)
##STR00016## [0058] R.sup.5 and R.sup.6 are hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, [0059] wherein
[0060] n is 1 or 2 and [0061] m is 1 or 2, [0062] with the proviso
that at least one of R.sup.5 and R.sup.6 is not hydrogen, [0063]
R.sup.7 is ethyl or methyl and [0064] X.sup.5 is hydrogen, bromo,
chloro, nitro or cyano, [0065] X.sup.6 is hydrogen, nitro or cyano,
[0066] with the proviso that X.sup.5 and X.sup.6 are not both nitro
[0067] and [0068] L is hydrogen or [0069] in case X.sup.6 is nitro
and X.sup.5 is hydrogen L is hydrogen or fluoro forms another
preferred embodiment of the present invention.
[0070] A dye mixture as described above, wherein the at least one
dye of formula (2) is a dye of formula (2c)
##STR00017##
wherein independent from each other R.sup.2 is hydrogen or
--NHCO--(C.sub.1-C.sub.2)-alkyl, R.sup.5 and R.sup.6 is hydrogen,
(C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, [0071] wherein
[0072] n is 1 or 2 and [0073] m is 1 or 2 with the proviso that at
least one of R.sup.5 and R.sup.6 is not hydrogen, X.sup.5 and
X.sup.6 is bromo or chloro, forms yet another preferred embodiment
of the present invention.
[0074] A dye mixture as described above, wherein the at least one
dye of formula (2) is a dye of formula (2d)
##STR00018##
wherein independent from each other R.sup.5 and R.sup.6 is
hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, [0075] wherein
[0076] n is 1 or 2 and [0077] m is 1 or 2 with the proviso that at
least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.7 is ethyl
or methyl R.sup.10 is hydrogen, methyl or methoxy, X.sup.6 is
chloro, bromo, nitro or cyano, and L is hydrogen or in case X.sup.6
is nitro L is hydrogen or fluoro, forms still another preferred
embodiment of the present invention.
[0078] Most preferred is a dye mixture as described above, wherein
the at least one dye of formula (2) is selected from the group
consisting of
##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023##
##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028##
##STR00029##
[0079] Also, regarding the number of different dyes selected from
the ones shown above there exist preferred dye mixtures:
[0080] Preferred are dye mixtures comprising one dye of formula (1)
and one dye of formula (2).
[0081] Preferred are dye mixtures comprising two dyes of formula
(1) and one dye of formula (2).
[0082] Preferred are dye mixtures comprising one dye of formula (1)
and two dyes of formula (2).
[0083] And preferred are dye mixtures comprising two dyes of
formula (1) and two dyes of formula (2)
[0084] Those dye mixtures as described above are particularly
preferred, wherein preferred dyes of formula (1) and preferred dyes
of formula (2) are combined, such as a dye mixture, wherein
independent from each other
R.sup.1 is hydrogen, methyl or methoxy, R.sup.2 is hydrogen,
hydroxy, COOH, COO--(C.sub.1-C.sub.2)-alkyl,
(C.sub.1-C.sub.2)-alkyl, --NHCO--(C.sub.1-C.sub.2)-alkyl,
--NHCO-aryl, --NHCO-benzyl or
--NHSO.sub.2--(C.sub.1-C.sub.2)-alkyl, R.sup.3 to R.sup.6 is
hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-phenyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O-benzyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, (CH.sub.2).sub.n--O--CO-benzyl,
COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, [0085] wherein
[0086] n is 1 or 2 and [0087] m is 1 or 2, with the proviso that
R.sup.3 and R.sup.4 in formula (1) are not
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl and that at least
one of R.sup.3 and R.sup.4 in formula (1) and at least one of
R.sup.5 and R.sup.6 in formula (2) is not hydrogen, R.sup.10 is
hydrogen, methyl or methoxy, R.sup.11 is hydrogen, hydroxy, COOH,
COO--(C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkyl,
--NHCO--(C.sub.1-C.sub.2)-alkyl, --NHCO-aryl, --NHCO-benzyl or
--NHSO.sub.2--(C.sub.1-C.sub.2)-alkyl, X.sup.5 and X.sup.6 is
hydrogen, chloro, bromo, nitro or cyano, with the proviso that at
least one of X.sup.5 and X.sup.6 in formula (2) is not hydrogen and
L is hydrogen or in case X.sup.6 is nitro and X.sup.5 is hydrogen L
is hydrogen or fluoro.
[0088] Accordingly, even more preferred is a dye mixture as
described above, wherein independent from each other
R.sup.1 is hydrogen or methoxy, R.sup.2 is hydrogen, methyl or
--NHCO--(C.sub.1-C.sub.2)-alkyl, R.sup.3 to R.sup.6 is hydrogen,
C.sub.1-C.sub.2-alkyl, (CH.sub.2)-phenyl,
CH.sub.2--CH.dbd.CH.sub.2,
(CH.sub.2).sub.2--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.2--O-phenyl, (CH.sub.2).sub.2--O-benzyl,
(CH.sub.2).sub.2--O--(CH.sub.2).sub.m--O--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO-phenyl, (CH.sub.2).sub.n--COO-benzyl,
(CH.sub.2).sub.n--CN,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl,
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-benzyl,
(CH.sub.2).sub.n--O--CO--(C.sub.1-C.sub.2)-alkyl,
(CH.sub.2).sub.n--O--CO-phenyl, COO--(CH.sub.2).sub.n-2-furfuryl or
(CH.sub.2).sub.m--O--(CH.sub.2).sub.n-2-furfuryl, [0089] wherein
[0090] n is 1 or 2 and [0091] m is 1 or 2, with the proviso that
R.sup.3 and R.sup.4 in formula (1) are not
(CH.sub.2).sub.n--COO(CH.sub.2).sub.m--CO-phenyl and that at least
one of R.sup.3 and R.sup.4 in formula (1) and at least one of
R.sup.5 and R.sup.6 in formula (2) is not hydrogen, R.sup.10 is
hydrogen or methoxy, R.sup.11 is hydrogen, methyl or
--NHCO--(C.sub.1-C.sub.2)-alkyl, X.sup.5 and X.sup.6 is hydrogen,
bromo, chloro, nitro or cyano, with the proviso that at least one
of X.sup.5 and X.sup.6 in formula (2) is not hydrogen and L is
hydrogen or in case X.sup.6 is nitro and X.sup.5 is hydrogen L is
hydrogen or fluoro.
[0092] Particularly preferred is a dye mixture as described above
comprising at least one dye of formula (1a) and at least one dye of
formula (2a).
[0093] Also, particularly preferred are dye mixtures comprising:
[0094] at least one dye of formula (1a) and at least one dye of
formula (2b), [0095] at least one dye of formula (1a) and at least
one dye of formula (2c), [0096] at least one dye of formula (1a)
and at least one dye of formula (2d), [0097] at least one dye of
formula (1b) and at least one dye of formula (2a), [0098] at least
one dye of formula (1b) and at least one dye of formula (2b),
[0099] at least one dye of formula (1b) and at least one dye of
formula (2c), [0100] at least one dye of formula (1b) and at least
one dye of formula (2d)
[0101] Most preferred is a dye mixture comprising at least one dye
selected from the list consisting of dyes (1-1) to (1-43) as
described above and at least one dye selected from the list
consisting of dyes (2-1) to (2-54).
[0102] Also preferred is a dye mixture as described above,
comprising one or more dyes selected from the group consisting of
dyes of formulae (3), (4) and (5),
##STR00030##
wherein independent from each other X.sup.4 is hydrogen or nitro,
Y.sup.2 is (C.sub.1-C.sub.4)-alkyl, phenyl or
(CH.sub.2).sub.m-phenyl, Y.sup.4 is (C.sub.1-C.sub.8)-alkyl or
(CH.sub.2).sub.m-phenyl, Y.sup.6 is hydrogen, nitro, cyano,
carboxy, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkoxy and m
is 1 to 4.
[0103] More preferred is a dye mixture as described above,
comprising one or more dyes selected from the group consisting of
dyes of formulae (3), (4) and (5) wherein
X.sup.4 is hydrogen or nitro, Y.sup.2 is (C.sub.1-C.sub.2)-alkyl or
(CH.sub.2).sub.m-phenyl, Y.sup.4 is (C.sub.1-C.sub.4)-alkyl or
(CH.sub.2)phenyl, Y.sup.6 is hydrogen, nitro, cyano or carboxy and
m is 1 or 2.
[0104] Even more preferred is a dye mixture as described above,
comprising one or more dyes selected from the group consisting of
dyes of formulae (3), (4) and (5) wherein
X.sup.4 is hydrogen or nitro, Y.sup.2 is (C.sub.1-C.sub.2)-alkyl or
(CH.sub.2).sub.m-phenyl, Y.sup.4 is (C.sub.1-C.sub.4)-alkyl or
(CH.sub.2).sub.m-phenyl, Y.sup.6 is hydrogen and m is 1 or 2.
[0105] A dye mixture as described above is particularly preferred
when comprising at least one dye of formula (3) selected from the
dyes consisting of
##STR00031##
[0106] A dye mixture as described above is particularly preferred
when comprising at least one dye of formula (4) selected from the
dyes consisting of
##STR00032##
[0107] A dye mixture as described above is particularly preferred
when comprising at least one dye of formula (5) selected from the
dyes consisting of
##STR00033##
[0108] The dyes of formula (1) and (2) are known and can be
prepared according to known procedures, for example from: U.S. Pat.
No. 4,619,993, DD 209 641 and EP 0 864 615.
[0109] The dyes of formula (3), (4) and (5) are known and can be
prepared according to known procedures, for example from the
documents: EP 0 440 072, DE 19 646 429, GB 2 300 863, U.S. Pat. No.
4,140,684 and DE 1544446.
[0110] A process for the production of a dye mixture as described
above, comprising [0111] a) mixing the dyes of formula (1) and (2)
and optionally the dyes of formula (3) and/or (4) and/or (5),
[0112] b) homogenising the mixture obtained in step a) forms
another aspect of the present invention.
[0113] The also exist preferred ranges of the amount of dyes in the
mixtures:
[0114] Ranges in weight % of the dye-components of the dye mixtures
as described above are preferably:
Dye(s) of formula 1: 10 to 90, Dye(s) of formula 2: 90 to 10.
[0115] More preferred are:
Dye(s) of formula 1: 25 to 75, Dye(s) of formula 2: 75 to 25.
[0116] The amounts of dyes of formula (1) and of formula (2) add up
to 100 wt % in those cases where no additional dyes are present in
the dye mixtures. In those cases where other dyes--and preferably
those selected from the dyes of formulae (3), (4) and (5)--are
present, the amount of dyes preferably is as follows:
Dye(s) of formula 1: 10 to 80, Dye(s) of formula 2: 80 to 10, Other
dyes: 10 to 35, where again the sum of all dyes present adds up to
100 wt %.
[0117] And more preferred:
Dye(s) of formula 1: 25 to 60, Dye(s) of formula 2: 60 to 25,
Dye(s) of formula 3, 4 and/or 5: 15 to 30, where again the sum of
all dyes present adds up to 100 wt %.
EXAMPLES
Example 1
[0118] a) 55 parts of a dye having formula (1-16) were mixed with
45 parts of a dye of the formula (2-2). The resulting dye mixture
of the invention was mixed intensively with 100 parts of a lignin
sulfonate dispersing agent (Reax 85A) and 300 parts of water. The
pH of the mixture is adjusted with diluted Sulfuric acid to
5.5+/-0.2 and the milled in a glass bead mill (0.4 to 0.7 mm glass
beads) for 4 to 6 hours to a size magnitude of 0.3 to 5
micrometres. The milled dye mixture slurry was filtrated from the
glass beads and spray dried in a lab spray dryer (Buchi) at
120.degree. C. inlet and 60 to 70.degree. C. outlet temperature.
[0119] b) 1 g of the dye mixture obtained as per a) are dispersed
in 100 ml of water at 40 to 50.degree. C. A dyebath is prepared
from 11.5 ml of this aqueous dispersion, 57.5 ml of deionized water
and 1.2 ml of buffering solution (pH 4.5) and entered with a 5 g
piece of polyester. The dyebath is heated to 130.degree. C. and
maintained at 130.degree. C. for 45 minutes in a Werner Mathis high
temperature dyeing machine. After rinsing with water and reduction
clearing, the polyester material has a gives blue/navy dyeing with
a good build up to deep shades, good light- and very good
wet-fastness.
Example 2
[0120] 30 parts dye of formula (1-15) were mixed with 30 parts of a
dye of formula (1-16) and with 40 parts of a dye powder of the
formula (2-28).
[0121] The resulting dye mixture of the invention was formulated
using dispersing agent and dried via spray drying according to
Example 1a) and gives blue/navy dyeing's on polyester or polyester
blends under the dyeing conditions according to 1b) with a good
light- and very good wet-fastness.
Example 3
[0122] 46 parts dye of formula (1-11) were mixed with 28 parts of a
dye of formula (2-1) and mixed with 26 parts of a dye powder of the
formula (2-30)
[0123] The resulting dye mixture of the invention was formulated
using dispersing agent and dried via spray drying according to
Example 1a) and gives reddish navy dyeing's on polyester or
polyester blends under the dyeing conditions according to 1b) with
a good light- and very good wet-fastness.
Example 4
[0124] 50 parts dye of formula (1-22) were mixed with 50 parts of a
dye of formula (2-26).
[0125] The resulting dye mixture of the invention was formulated
using dispersing agent and dried via spray drying according to
Example 1a) and gives blue dyeing's on polyester or polyester
blends under the dyeing conditions according to 1b) with good
light- and very good wet-fastness.
[0126] All examples of the following tables are prepared as
formulations as explained above.
TABLE-US-00001 Dye of formula Dye of formula Dye of formula Dye of
formula Ratio Shade on Example (1) (1) (2) (2) (1):(1):(2):(2)
Polyester 5 (1-11) -- (2-27) -- 75:--:25:-- Blue 6 (1-11) -- (2-26)
(2-27) 52:--:24:24 Blue 7 (1-22) -- (2-10) -- 25:--:75:-- Blue 8
(1-2) -- (2-5) -- 85:--:15:-- Blue 9 (1-5) -- (2-1) -- 50:--:50:--
Blue 10 (1-3) -- (2-20) -- 57:--:43:-- Red. Navy 11 (1-4) -- (2-50)
-- 87:--:13:-- Red. Navy 12 (1-8) -- (2-26) -- 60:--:40:-- Blue 13
(1-8) (1-11) (2-30) -- 50:40:10:-- Navy 14 (1-11) -- (2-34) --
67:--:33:-- Black 15 (1-22) (1-11) (2-35) -- 30:40:30:-- Black 16
(1-13) -- (2-44) (2-33) 40:--:31:29 Black 17 (1-11) -- (2-2) (2-29)
35:--:31:34 Black 18 (1-9) (1-11) (2-26) (2-33) 28:28:14:30 Black
19 (1-7) -- (2-2) (2-30) 36:--:45:19 Red. Navy 20 (1-11) (1-22)
(2-1) (2-26) 28:28:34:10 Red. Navy 21 (1-24) -- (2-43) --
76:--:24:-- Navy 22 (1-22) -- (2-30) -- 66:--:34:-- Violet 23
(1-22) (1-24) (2-31) -- 43:40 :17:-- Red. Navy 24 (1-37) -- (2-30)
-- 80:--:20:-- Red 25 (1-38) -- (2-50) -- 74:--:26:-- Redviolet Dye
of Dye of Dye of Dye of Dye of Dye of Dye of formula formula
formula formula formula formula formula Ratio Shade on Example (1)
(1) (2) (2) (3) (4) (5) (1):(1):(2):(2):(3):(4):(5) Polyester 26
(1-11) -- (2-1) -- (3-1) -- (5-1) 37:--:30:--:22:--:11 Black 27
(1-22) -- (2-27) -- (3-2) (4-1) 60:--:20:--:12:8:-- Black 28 (1-24)
-- (2-1) (2-35) -- -- (5-2) 38:--:22:28:--:--:12 Black 29 (1-9)
(1-29) (2-48) (2-31) (3-1) (4-2) (5-1) 28:12:18:10:20:6:6 Black 30
(1-4) (1-11) (2-30) -- (3-2) -- (5-1) 25:35:9:--:23:--:8 Black 31
(1-22) -- (2-2) -- (3-1) -- (5-1) 46:--:28:--:17:--:9 Black 32
(1-29) -- (2-2) -- (3-3) -- -- 25:--:58:--:17:--:-- Black 33 (1-29)
(1-9) (2-44) -- (3-2) (4-1) -- 32:15:16:--:28:9:-- Black 34 (1-23)
-- (2-35) -- -- -- (5-1) 62:--:25:--:--:--:13 Black 35 (1-22)
(1-24) (2-30) -- (3-1) -- -- 35:35:10:--:20:--:-- Black
[0127] When the dye mixture of the present invention is used in
dyeing, the dye mixture is dispersed in an aqueous medium by means
of a dispersing agent and wetting agent in the usual way to prepare
a dye bath for dyeing or a printing of hydrophobic
textile-fibres.
[0128] And also, the use of a dye mixture as described above for
dying fibres, as well as blends of such fibres forms an aspect of
the present invention.
[0129] The synthetic textile material may preferably be selected
from aromatic polyester, especially polyethylene terephthalate,
polyamide, especially polyhexamethylene adipamide, secondary
cellulose acetate, cellulose triacetate, and natural textile
materials, especially cellulosic materials and wool. An especially
preferred textile material is an aromatic polyester or fibre blend
thereof with fibres of any of the above-mentioned textile
materials. Especially preferred fibre blends include those of
polyester-cellulose, such as polyester-cotton, and
polyester-wool.
[0130] The textile materials or blends thereof may be in the form
of filaments, loose fibres, yarn or woven or knitted fabrics.
[0131] Particularly, among polyester fibres, not only ordinary
polyester fibres (regular denier fibres) but also microfibres (fine
denier fibres, which are less than 0.6 denier) may be used as
fibres which can successfully be dyed with the dye mixture of the
present invention.
[0132] In general all kinds of fibres can be dyed and therefore
fibre and blends containing such fibre selected from the group
consisting of: synthetic fibre materials, nylon materials, nylon-6,
nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton,
organic cotton, kapok, coir from coconut husk; bast fibres, flax,
hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen,
banana; stalk fibres, bamboo; fibres from animals, wool, organic
wool, silk, cashmere wool, alpaca fibre, mohair, Angora fibre as
well as fur and leather materials; manufactured, regenerated and
recycled fibres, cellulosic fibres; paper fibres, cellulosic
regenerated fibres, viscose rayon fibres, acetate and triacetate
fibres, and Lyocell fibres comprising a dye mixture as described
above either in chemically and/or physically bound form forms/form
another aspect of the present invention.
[0133] Typical examples of dispersing agent are lignosulphonates,
naphthalene sulphonic acid/formaldehyde condensates and
phenol/cresol/sulphanilic acid/formaldehyde condensates, typical
examples of wetting agent are alkyl aryl ethoxylates which may be
sulphonated or phosphated and typical example of other ingredients
which may be present are inorganic salts, de-dusting agents such as
mineral oil or nonanol, organic liquids and buffers. Dispersing
agents may be present at from 30 to 500% based on the weight of the
dye mixture. Dedusting agents may be used at from 0 to 5% based on
the weight of the dye mixture.
[0134] A process for dyeing or printing carboxamido- and/or
hydroxyl-containing material, comprising contacting the
carboxamido- and/or hydroxyl-containing material with a dye mixture
as described above and/or an aqueous solution as described above
forms yet another aspect of the present invention.
[0135] For example, in the case of dyeing polyester fibres and
fibre mixture products such as blended yarn fabrics of union cloth
product comprising polyester fibres can be dyed with good colour
fastness by common dyeing methods, such as a high temperature
dyeing method, a carrier dyeing method and a thermosol dyeing
method. In some cases, the addition of an acid substance to the dye
bath may result in even more successful dyeing.
[0136] Suitable process conditions may be selected from the
following [0137] (i) exhaust dyeing at a pH of from 4 to 8.5, at a
temperature of from 125 to 140.degree. C. for from 10 to 120
minutes and under a pressure of from 1 to 2 bar, a sequestrant
optionally being added; [0138] (ii) continuous dyeing at a pH of
from 4 to 8.5, at a temperature of from 190 to 225.degree. C. for
from 15 seconds to 5 minutes, a migration inhibitor optionally
being added; [0139] (iii) direct printing at a pH of from 4 to 6.5,
at a temperature of from 160 to 185.degree. C. for from 4 to 15
minutes for high temperature steaming, or at a temperature of from
190 to 225.degree. C. for from 15 seconds to 5 minutes for bake
fixation with dry heat or at a temperature of from 120 to
140.degree. C. and 1 to 2 bar for from 10 to 45 minutes for
pressure steaming, wetting agents and thickeners (such as
alginates) of from 5 to 100% by weight of the dye optionally being
added; [0140] (iv) discharge printing (by padding the dye on to the
textile material, drying and overprinting) at a pH of from 4 to
6.5, migration inhibitors and thickeners optionally being added;
[0141] (v) carrier dyeing at a pH of from 4 to 7.5, at a
temperature of from 95 to 100.degree. C. using a carrier such as
methylnaphthalene, diphenylamine or 2-phenylphenol, sequestrants
optionally being added; and [0142] (vi) atmospheric dyeing of
acetate, triacetate and nylon at a pH of from 4 to 7.5, at a
temperature of about 85.degree. C. for acetate or at a temperature
of about 90.degree. C. for triacetate and nylon for from 15 to 90
minutes, sequestrants optionally being added.
[0143] In all the above processes, the dye mixture is applied as a
dispersion comprising from 0.001 to 20 wt. %, preferably from 0.005
to 16 wt. %, of the dye mixture in an aqueous medium.
[0144] In addition to the above-mentioned application processes,
the dye mixture may be applied to synthetic textile materials and
fibre blends by ink-jet printing, the substrates optionally having
been pre-treated to aid printing.
[0145] An ink for digital textile printing, comprising a dye
mixture as described above is another aspect of the present
invention.
[0146] For ink-jet applications, the application medium may
comprise water and a water-soluble organic solvent, preferably in a
weight ratio of 1:99 to 99:1, more preferably 1:95 to 50:50 and
especially in the range 10:90 to 40:60. The water-soluble organic
solvent preferably comprises a C.sub.1-C.sub.4-alkanol, especially
methanol or ethanol, a ketone, especially acetone or methyl ethyl
ketone, 2-pyrrolidone or N-methylpyrrolidone, a glycol, especially
ethylene glycol, propylene glycol, trimethylene glycol,
butane-2,3-diol, thiodiglycol or diethylene glycol, a glycol ether,
especially ethylene glycol monomethyl ether, propylene glycol
monomethyl ether or diethylene glycol monomethyl ether, urea, a
sulphone, especially bis-(2-hydroxyethyl) sulphone or mixtures
thereof.
[0147] The dyestuff may also be applied to textile materials using
supercritical carbon dioxide, in which case the dye formulating
agents may optionally be omitted.
* * * * *